Darstellung und Charakterisierung substituierter Phosphinoether und -thioether / Preparation and Characterization of Substituted Phosphinoethers and -thioethers

Abstract

The (diorganophosphinopropyl)alkyl ethers 1-7 are prepared by hydrophosphination of allylalkyl ethers with secondary phosphines. The corresponding thioethers cannot be obtained in a pure state by the same route. The nucleophilic ring opening of thiirane with lithium dialkyl phosphides, followed by the reaction with ClSi(CH3)3 or Cl(CH2)2OCH3 produces the thioethers 8-12 and 16. The silylated thioethers 8, 10 and 12 react with CH3OH/H2O to give the phosphinoethyl thiols 13-15. All new compounds have been identified and characterized by elemental analyses, IR and NMR spectra.

Synthesis and Characterization of Triosmium Clusters Containing the Bidentate Ligand Ph2PCH2CH2SMe: Detection of an Isomerization Reaction Involving Bridging and Chelating Ligand Coordination Modes

“…The chemistry of asymmetric bidentate ligands is receiving considerable attention and a number of transition metal complexes containing bi- or polydentate phosphine-based ligands, e.g., phosphine-amine (P,N), phosphine-ether (P,O), and phosphine-thiolate or phosphine-thioether (P,S) 3 ligands, have been reported in recent years. Many such metal complexes act as modest to good catalysts in different asymmetric transformations, e.g., allylic alkylations, hydrogenations, and Heck reactions. − The coordination chemistry of phosphine-ether and phosphine-thioether ligands, including chiral ligands, has been studied by several investigators. 3b,− For example, it has been found that the phosphine i Pr 2 PCH 2 CH 2 OMe may coordinate in unidentate (through the phosphorus atom) and bidentate coordination modes in Ru(II) complexes; examples include [RuCl 2 (CO) 2 (η 1 - i Pr 2 PCH 2 CH 2 OMe) 2 ], [RuCl 2 (η 2 - i Pr 2 PCH 2 CH 2 OMe) 2 ], and [RuCl 2 (η 2 -Ph 2 PCH 2 CH 2 OMe) 2 ] . Mononuclear transition metal (e.g., Mo, Rh, Ir) complexes containing the related P,S ligand Ph 2 PCH 2 CH 2 SMe have also been reported …”